Phosphoro carbimidates



United States 3,070,493 PHOSPHORO CARBIMIDATES Glenn R. Price, SouthChicago Heights, and Edward N. Walsh, Chicago Heights, 111., and JamesT. Hallett, Saratoga, Califl, assignors to Staufier Chemical Compauy,New York, N.Y., a corporation of Delaware No Drawing. Filed Apr. 10,1961, Ser. No. 101,673

23 Claims. (Cl. 167-30) This invention relates to .a new class ofphosphor-us containing pesticides and a process for utilizing the same.

In particular this invention relates to new compounds having a noveldisulfide configuration which provides new and valuable characteristics.These new compounds have been found to be useful in the elimination andcontrol of numerous insect pests as will be shown hereafter.

These new compounds are phosphoro carbimidates which may be representedby the formula:

R10 NR wherein R and R are the same or difierent alkyl redicals, R maybe alkyl or iaryl, R may be alkyl or aryl and X is oxygen or sulfur.They may be prepared according to the following general reaction:

P(O)SY RgNHC (S)XR4 RE (R10) NR3 P (O)SSC RsN-HY wherein R R R R and Xare as defined above, Y is a halogen, and R N is a tertiary aminehydrogen halide acceptor.

Among the alkyl radicals which we have found suitable for the phosphorusester portion of the molecule are the methyl, ethyl, propyl, butyl,octyl, and decyl radicals as well as combinations resulting in mixedesters such as methyl ethyl, ethyl octyl, methyl, butyl, ethyl propyland the like. Suitable alkyl or aryl radicals for R and R includemethyl, ethyl, propyl, butyl, octyl, phenyl, chlorophenyl, nitrophenyland the like.

The hydrogen halide acceptor may be any of the wellknown alkalinecompounds suitable for this use. In particular we prefer to use tertiaryamines such as pyridine, triethylamine, trimethylamine and the like.

The process is preferably carried out in an inert solvent in thepresence of the hydrogen halide acceptor by adding approximatelystoichiometric amounts of 0,0-dialkylphosphorosulfenyl halide to theappropriate thiocarbamate. The reaction is nearly instantaneous attemperatures from about 0 C. to ordinary room temperature, although itis best to stir the final thickened reaction mixture for a short whileto ensure complete reaction. The prodnot is then recovered by filteringoff the halide salt or by other well-known means such as washing out thesalt.

The following examples illustrate the compounds of our invention:

EXAMPLE 1 To a solution of 7.9 grams oi:'-pyridine and 18.1 grams ofN-phenyl-O-ethyl-thiocarbamate in 200 cc. 'of ether was added 20.4 gramsof 0,0-diethylphosphorosulfenyl chloride over a minute period at 10 C.The crude product was stirred for two hours at room temperature and thenfiltered to remove the pyridine hydrochloride. The crude product wasstabilized to 50 C. at 1.0 mm. of Hg to yield 30.5 grams (87% yield).The product ana- P and 19.1% S theoretical.

"ice

2. lyzed as 10.0% P and 21.6% S compared to 10.7% P and 22.1% Stheoretical for NCaHs (02H5o.)a1 (0)s-s-0 EXAMPLE 2 Following theprocedure of Example 1, but using N-pchlorophenyl-O-ethylthiocarbam-ate, 36 grams (96%) of (oiHtm r(0)- s s o=NotHio1 (I) CzHswas prepared which analyzed 7.4% P and 16.0% S compared to 8.1% P and16.7% S theoretical. I

EXAMPLE 3 Following the procedure of Example 1 but using N-phenyl-O-methyl thiocarbamate, 60.0 grams (92%) of(G2H5O)2'P(O)-S-SC=NC0H5 CH3 was prepared which had an index ofrefraction and analyzed 8.6% P and 18.7% S compared to 9.25%

v EXiAM-PLE'4 In a similar manner but using N-phenyl O-isopropylthiocarbamate, a yield of product was obtained. This material analyzedas 8.55% P and 17.4% S compared with 8.5% P and 17.6% S theoretical forC2H50)2P (O)SSC=NCBH5 OC3H1 EXAMPLE 5 Following the procedure of Example1 but using 0,0- dimethylphosphorosulfenyl chloride, 57 grams (93%yield) of OH.o)iP(0)-s-so=NCiH.

OCzHa was prepared which analyzed as 8.9% P 18.8% S compared with 9.65%P and 19.9% S theoretical.

EXAMPLE 6 In a similar manner (C H OMP (O)s-SC NC6H5 O CH:

was made in 84.5% yield, N 35=1.5-1:24, analysis 6.05% P and 12.5% S(theoretical 6.16% P, 12.7%. S).

EXAMPLE 7 In a similar manner (CsHnO) (021350) P (O).-S -S C=NCOH5 0011(0113): was made in 99% yield, N =1.5176.

EXAMPLE 8 To a solution of 29.7 grams of N-phenyl-S-ethyldithioc-arbamate in ml. of ether was added 15.2 grams of.triethylarnine. The solution was cooled to 10 C. and 30.6 grams of0,0-diethylphosphorosulfenyl chloride was added over a 30 minute period.The reaction mixture was stirred for an additional hour at roomtemperature and then at reflux for 30 minutes. After filtering andremoving the solvent, the product was stabilized to 50 C. at 1.0 mm. Hgpressure. A yield of 51.5 grams (95.5%) was obtained with an index ofrefraction N ==1.5802 and Patented Dec. 25. 1962 Q which analyzed 7.32%P and 26.4% S compared to 8.5% P and 26.3% S for was prepared which hadan index of refraction and analyzed as 7.5% P and 25.2% S compared to8.5%

P and 26.3% S theoretical.

Using the process as outlined above the following additional compoundswere made.

water. The latter contains 2.5 grams of Vatsol and 1.0 gram of Methocelper liters of water. Each solution is then sprayed onto the insectsusing a DeVilbiss hand sprayer in a fume hood. Mortality is reportedafter 72 hours as percent kill/percent concentration.

In addition to the above insects, tests were also run on the two-spottedmite, Tetranychus telarius (designated 28M) and the effects wereadditionally noted on the eggs (designated 2SME). The tests wereconducted by infesting young Pinto bean plants in the primary leaf stagewith several hundred mites. The infested plants were then sprayed torun-off using the sprayer and solutions previously described. Theresults are again reported as percent kill/percent concentration. Themiticidal activity is determined after seven days but the ovicidalresults require fourteen days.

The following results were obtained using the compounds of thisinvention.

Theoretical Example R; R: R: X B4 N 1:

Per-

Percent S oooooooooommmm The class of compounds characterized by theforegoing examples has been found to have valuable pesticidalproperties. In particular, these compounds are valuable in the controlof common insect pests. By the term insect we do not intend to belimited to the narrow technical usage of this term to include onlysix-legged pests but intend the broader more common usage which includesspiders, mites, ticks, caterpillars, nematodes and the like.

In the following described tests demonstrating the utility of our newcompounds, four insect species representing four insect orders wereused. These species are:

( 1) American cockroach-Periplanela arnericana-Orthoptera (designatedAR) (2) Confused flour beetleTrib0lium confusum-Coleoptera (designatedCFB) (3) House fiy-Musca domestica-Diptera (designated (4) Spottedmilkweed bug0ncopelms fasciatusI-Ieteroptera (designated MWB) Inconducting the tests, the compounds are made up into solutions, normally0.1% concentration, using wet 28M 28MB From these data it can be seenthat these new compounds are valuable insecticides. Although thespecific examples show the use of aqueous solutions of these compoundsas insecticides, they may also be used in the form of emulsions,non-aqueous solutions, wettable powders, vapors, and dusts as may bebest fitted to the conditions of use.

The concentration normally used for initial testing is a 0.1% solution.As noted above, however, many of these new compounds are effectivepesticides at much lower levels, as low as 0.000l% in some instances.Since the efiective concentration may vary with each compound and eachpest to which it is applied, a general numerical range of concentrationscannot be stated. It is well within the skill of the art, however, todetermine the effective concentration necessary to kill a significantproportion of a specific pest or combination of pests under certainconditions of application.

The foregoing description is given for clearness of understanding onlyand no unnecessary limitations should be understood therefrom asmodification will be obvious to those skilled in the art.

We claim:

1. Compounds having the formula R20 XR4 wherein R and R are alkylradicals, R and R are members of the class consisting of lower alkyl,phenyl and substituted phenyl radicals and X is a member of the classconsisting of oxygen and sulfur.

2. The compound represented by formula 3. The compound represented bythe formula NCuH4C1 (ClH50):P(O)-SSC OCZH;

. The compound represented by the formula NCoHi (C:HsO):P(0)S-SC 5. Thecompound represented by the formula NGoH (CflHltO)2P(O)-SS0 O C3H7 6.The compound represented by the formula N C Hu (C2H50)IP (O)-SSC OCzHIThe compound represented by the formula NC H:

(CQH50)2P(O)-SSG 8. The compound represented by the formula Noni,(CzHsOhP (O)SS-C O CzHs The compound represented by the formula NClHfl(C2HsO)2P (O)S-SC OCH:

12. A process for controlling pests comprising applying thereto anelfective concentration of a compound represented by the formula whereinR and R are alkyl radicals, R and R are members of the class consistingof lower alkyl, phenyl and substituted phenyl radicals and X is a memberof the class consisting of oxygen and sulfur.

13. A process for controlling pests comprising applying thereto aneffective concentration of the compound of claim 2.

14. A process for controlling pests comprising applying thereto anefiective concentration of the compound of claim 3.

15. A process for controlling pests comprising applying thereto aneffective concentration of the compound of claim 4.

16. A process for controlling pests comprising applying thereto aneffective concentration of the compound of claim 5.

17. A process for controlling pests ing thereto an etfectiveconcentration of claim 6.

18. A process for controlling pests comprising applying thereto aneffective concentration of the compound of claim 7.

19. A process for controlling pests ing thereto an effectiveconcentration of claim 8.

20. A process for controlling pests ing thereto an elfectiveconcentration of claim 9.

p 21. A process for controlling pests comprising applying thereto aneffective concentration of the compound of claim 10.

22. A process for controlling pests ing thereto an effectiveconcentration of claim 11.

23. A process for preparing compounds having the formula comprisingapplyof the compound comprising applyof the compound comprising applyofthe compound comprising applyof the compound P-SS--C=N.Ra

R20 XR4 wherein R and R are alkyl radicals, R and R are members of theclass consisting of lower alkyl, phenyl and substituted phenyl radicalsand X is a member of the class consisting of oxygen and sulfur, whichcomprises reacting substantially stoichiometric quantities of a compoundhaving the formula Rio P(O)SY R20 wherein Y is a halogen atom with acompound having the formula R NHC(S)XR in the presence of a hydrogenhalide acceptor.

No references cited.

1.COMPOUNDS HAVING THE FORMULA